Reactive Uptake Of Isoprene Epoxydiols Research Articles

Applying a Phase-Separation Parameterization in Modeling Secondary Organic Aerosol Formation from Acid-Driven Reactive Uptake of Isoprene Epoxydiols under Humid Conditions.

Secondary organic aerosol (SOA) from acid-driven reactive uptake of isoprene epoxydiols (IEPOX) contributes up to 40% of organic aerosol (OA) mass in fine particulate matter. Previous work showed that IEPOX substantially converts particulate inorganic sulfates to surface-active organosulfates (OSs). This decreases aerosol acidity and creates a viscous organic-rich shell that poses as a diffusion barrier, inhibiting additional reactive uptake of IEPOX. To account for this "self-limiting" effect, we developed a phase-separation box model to evaluate parameterizations of IEPOX reactive uptake against time-resolved chamber measurements of IEPOX-SOA tracers, including 2-methyltetrols (2-MT) and methyltetrol sulfates (MTS), at ~ 50% relative humidity. The phase-separation model was most sensitive to the mass accommodation coefficient, IEPOX diffusivity in the organic shell, and ratio of the third-order reaction rate constants forming 2-MT and MTS ( ). In particular, had to be lower than 0.1 to bring model predictions of 2-MT and MTS in closer agreement with chamber measurements; prior studies reported values larger than 0.71. The model-derived rate constants favor more particulate MTS formation due to 2-MT likely off-gassing at ambient-relevant OA loadings. Incorporating this parametrization into chemical transport models is expected to predict lower IEPOX-SOA mass and volatility due to the predominance of OSs.

Identification and quantification of IEPOX in ambient aerosols, using electron and chemical ionization sources GC/MS as their trimethylsilyl ethers, and using H-NMR

Isoprene is the most abundant non-methane hydrocarbon (NMHC) emitted by vegetation, and the precursor that makes the greatest contribution to secondary organic aerosols (SOA) in the troposphere. Atmospheric oxidation of isoprene produces a series of reactive intermediates, isoprene epoxydiols (IEPOX). The reactive uptake of IEPOX is the significant formation pathway of atmospheric SOA. In this work, four isomers of IEPOX were synthesized, derivatized by silylation reagents, and measured by gas chromatography/mass spectrometry (GC/MS). The electron-impact (EI) and methane chemical ionization (CI) sources mass spectra of trimethylsilyl ester (TMS) derivatives of IEPOX isomers were obtained and the fragmentation behaviors of the derivatives were examined. Moreover, the hydrogen nuclear magnetic resonance (H-NMR) spectra of IEPOX isomers were also obtained and the peak intensities in the H-NMR spectra were analyzed. Based on the standard spectra, IEPOX isomers were identified in ambient PM2.5 aerosols in the Gongga Mountain (China). The peak sequence of TMS derivatives of IEPOX isomers in GC/MS chromatogram was δ4-IEPOX, δ1-IEPOX, cis-β-IEPOX and trans-β-IEPOX. The isomers with the highest concentrations were δ1-IEPOX (threo- and erythro-). The mass ratios of IEPOX to 2-methyltetrols were 0.02–6.0 and the concentrations of IEPOX were 0.8–41.6 ng/m3 in the PM2.5 aerosols. The current study verified the core roles of IEPOX as active intermediates in photo oxidation of isoprene in ambient atmosphere.

Organosulfate Formation in Proxies for Aged Sea Spray Aerosol: Reactive Uptake of Isoprene Epoxydiols to Acidic Sodium Sulfate

Organosulfate Formation in Proxies for Aged Sea Spray Aerosol: Reactive Uptake of Isoprene Epoxydiols to Acidic Sodium Sulfate

Morphology and Viscosity Changes after Reactive Uptake of Isoprene Epoxydiols in Submicrometer Phase Separated Particles with Secondary Organic Aerosol Formed from Different Volatile Organic Compounds

Morphology and Viscosity Changes after Reactive Uptake of Isoprene Epoxydiols in Submicrometer Phase Separated Particles with Secondary Organic Aerosol Formed from Different Volatile Organic Compounds

Decrease in sulfate aerosol light backscattering by reactive uptake of isoprene epoxydiols.

Sulfate aerosol is responsible for a net cooling of the Earth's atmosphere due to its ability to backscatter light. Through atmospheric multiphase chemistry, it reacts with isoprene epoxydiols leading to the formation of aerosol and organic compounds, including organosulfates and high-molecular weight compounds. In this study, we evaluate how sulfate aerosol light backscattering is modified in the presence of such organic compounds. Our laboratory experiments show that reactive uptake of isoprene epoxydiols on sulfate aerosol is responsible for a decrease in light backscattering compared to pure inorganic sulfate particles of up to - 12% at 355 nm wavelength and - 21% at 532 nm wavelength. Moreover, while such chemistry is known to yield a core-shell structure, the observed reduction in the backscattered light intensity is discussed with Mie core-shell light backscattering numerical simulations. We showed that the observed decrease can only be explained by considering effects from the complex optical refractive index. Since isoprene is the most abundant hydrocarbon emitted into the atmosphere, and isoprene epoxydiols are the most important isoprene secondary organic aerosol precursors, our laboratory findings can aid in quantifying the direct radiative forcing of sulfates in the presence of organic compounds, thus more clearly resolving the impact of such aerosol particles on the Earth's climate.

Mixing order of sulfate aerosols and isoprene epoxydiols affects secondary organic aerosol formation in chamber experiments

The reactive uptake of isoprene epoxydiols (IEPOX) is a significant source of isoprene-derived secondary organic aerosols (SOA). Multiple field studies have reported that summertime isoprene-derived SOA in the Southeastern U.S. correlated strongly with sulfate mass concentration. However, previous laboratory studies have focused largely on the effect of aerosol acidity on the reactive uptake of IEPOX. In this study, we investigated the role of inorganic sulfate aerosols in SOA formation arising from the reactive uptake of trans-β-IEPOX (the predominant IEPOX isomer) at 50–56% RH in laboratory chamber experiments. Our measurements showed that the SOA mass concentration increased with the sulfate mass for both highly acidic and less acidic seed aerosols. This was due to the roles that sulfate played in SOA formation as a particle-phase reactant and as a contributor to aerosol surface area and volume. Higher concentrations of SOA were formed when highly acidic seed aerosols were used, consistent with previous laboratory studies. SOA mass concentration and composition were also observed to be dependent on the injection order of IEPOX and sulfate seed aerosols (i.e., injection of IEPOX first vs. Injection of seed aerosols first) in the chamber experiments. Higher SOA mass concentrations were measured in experiments where sulfate seed aerosols were introduced into the chamber first, followed by IEPOX. Volatility measurements showed that the SOA formed in the “seed aerosols first” experiments likely contained larger quantities of low volatility organic matter compared to SOA formed in the “IEPOX first” experiments. These results showed that the mass concentration and composition of IEPOX-derived SOA formed in chamber experiments can be sensitive to mixing conditions in the chamber brought about by slight differences in experimental methodology (in this case injection procedure). The sensitivity of SOA formation to the amount of seed aerosols and injection procedure used in chamber experiments indicated that caution should be exercised when extrapolating laboratory data to ambient conditions.

Isoprene-derived secondary organic aerosol in the global aerosol–chemistry–climate model ECHAM6.3.0–HAM2.3–MOZ1.0

Abstract. Within the framework of the global chemistry climate model ECHAM–HAMMOZ, a novel explicit coupling between the sectional aerosol model HAM-SALSA and the chemistry model MOZ was established to form isoprene-derived secondary organic aerosol (iSOA). Isoprene oxidation in the chemistry model MOZ is described by a semi-explicit scheme consisting of 147 reactions embedded in a detailed atmospheric chemical mechanism with a total of 779 reactions. Semi-volatile and low-volatile compounds produced during isoprene photooxidation are identified and explicitly partitioned by HAM-SALSA. A group contribution method was used to estimate their evaporation enthalpies and corresponding saturation vapor pressures, which are used by HAM-SALSA to calculate the saturation concentration of each iSOA precursor. With this method, every single precursor is tracked in terms of condensation and evaporation in each aerosol size bin. This approach led to the identification of dihydroxy dihydroperoxide (ISOP(OOH)2) as a main contributor to iSOA formation. Further, the reactive uptake of isoprene epoxydiols (IEPOXs) and isoprene-derived glyoxal were included as iSOA sources. The parameterization of IEPOX reactive uptake includes a dependency on aerosol pH value. This model framework connecting semi-explicit isoprene oxidation with explicit treatment of aerosol tracers leads to a global annual average isoprene SOA yield of 15 % relative to the primary oxidation of isoprene by OH, NO3 and ozone. With 445.1 Tg (392.1 Tg C) isoprene emitted, an iSOA source of 138.5 Tg (56.7 Tg C) is simulated. The major part of iSOA in ECHAM–HAMMOZ is produced by IEPOX at 42.4 Tg (21.0 Tg C) and ISOP(OOH)2 at 78.0 Tg (27.9 Tg C). The main sink process is particle wet deposition, which removes 133.6 (54.7 Tg C). The average iSOA burden reaches 1.4 Tg (0.6 Tg C) in the year 2012.

Source apportionment of submicron organic aerosol collected from Atlanta, Georgia, during 2014–2015 using the aerosol chemical speciation monitor (ACSM)

The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was redeployed at the Jefferson Street (JST) site in downtown Atlanta, Georgia (GA) for 1 year (March 20, 2014–February 08, 2015) to chemically characterize non-refractory submicron particulate matter (NR-PM1) in near real-time and to assess whether organic aerosol (OA) types and amounts change from year-to-year. Submicron organic aerosol (OA) mass spectra were analyzed by season using multilinear engine (ME-2) to apportion OA subtypes to potential sources and chemical processes. A suite of real-time collocated measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network was compared with ME-2 factor solutions to aid in the interpretation of OA subtypes during each season. OA tracers measured from high-volume filter samples using gas chromatography interfaced with electron ionization-mass spectrometry (GC/EI-MS) also aided in identifying OA sources. The initial application of ME-2 to the yearlong ACSM dataset revealed that OA source apportionment by season was required to better resolve sporadic OA types. Spring and fall OA mass spectral datasets were separated into finer periods to capture potential OA sources resulting from non-homogeneous emissions during transitioning periods. NR-PM1 was highest in summer (16.7 ± 8.4 μg m−3) and lowest in winter (8.0 ± 5.7 μg m−3), consistent with prior studies. OA dominated NR-PM1 mass (56–74% on average) in all seasons. Hydrocarbon-like OA (HOA) from primary emissions was observed in all seasons, averaging 5–22% of total OA mass. Strong correlations of HOA with carbon monoxide (CO) (R = 0.71–0.88) and oxides of nitrogen (NOx) (R = 0.55–0.79) indicated that vehicular traffic was the likely source. Biomass burning OA (BBOA) was observed in all seasons, with lower contributions (2%) in summer and higher in colder seasons (averaging 8–20% of total OA mass). BBOA correlated strongly with levoglucosan (R = 0.78–0.95) during colder seasons, which supports that BBOA is likely derived from fresh biomass/residential burning. However, weaker correlation with levoglucosan (R = 0.38) in summer suggested a more aged aerosol. During warmer seasons, OA from the reactive uptake of isoprene epoxydiols (IEPOX) onto acidic sulfate aerosol was resolved by ME-2 (denoted as IEPOX-OA), averaging 25–29% of the total OA mass. Temporal variation of IEPOX-OA was nearly coincident with that of 91Fac OA (a factor dominated by a distinct ion at m/z 91). The largest contribution of IEPOX-OA to total OA (29%) was found in summer, whereas the largest contribution of 91Fac to total OA (24%) occurred in early fall. Moderate negative correlation between IEPOX-OA and aerosol acidity was observed during late spring (−0.67) and summer (−0.42), consistent with laboratory studies showing that IEPOX-OA is enhanced in the presence of acidic aerosols. Finally, the largest OA mass in all seasons (46–70% of total OA) was derived from oxygenated OA denoted as low-volatility oxygenated OA (LV-OOA) and semi-volatile oxygenated OA (SV-OOA).

Enhanced formation of isoprene‐derived organic aerosol in sulfur‐rich power plant plumes during Southeast Nexus

AbstractWe investigate the effects of anthropogenic sulfate on secondary organic aerosol (SOA) formation from biogenic isoprene through airborne measurements in the southeastern United States as part of the Southeast Nexus (SENEX) field campaign. In a flight over Georgia, organic aerosol (OA) is enhanced downwind of the Harllee Branch power plant but not the Scherer power plant. We find that the OA enhancement is likely caused by the rapid reactive uptake of isoprene epoxydiols (IEPOX) in the sulfate‐rich plume of Harllee Branch, which was emitting at least 3 times more sulfur dioxide (SO2) than Scherer, and more aerosol sulfate was produced downwind. The contrast in the evolution of isoprene‐derived OA concentration between two power plants with different SO2 emissions provides an opportunity to investigate the magnitude and mechanisms of particle sulfate on isoprene‐derived OA formation. We estimate that 1 µg sm−3 reduction of sulfate would decrease the isoprene‐derived OA by 0.23 ± 0.08 µg sm−3. Based on a parameterization of the IEPOX heterogeneous reactions, we find that the effects of sulfate on isoprene‐derived OA formation in the power plant plume arises from enhanced particle surface area and particle acidity, which increases both IEPOX uptake to particles and subsequent aqueous‐phase reactions, respectively. The observed relationships between isoprene‐OA, sulfate, particle pH, and particle water in previous field studies are explained using these findings.

Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols.

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Contribution of Isoprene Epoxydiol to Urban Organic Aerosol: Evidence from Modeling and Measurements

In a region heavily influenced by anthropogenic and biogenic atmospheric emissions, recent field measurements have attributed one-third of urban organic aerosol by mass to isoprene epoxydiols (IEPOX). These aerosols arise from the gas-phase oxidation of isoprene, the formation of IEPOX, the reactive uptake of IEPOX by particles, and finally the formation of new compounds in the aerosol phase. Using a continental-scale chemical transport model, we find a strong temporal correspondence between the simulated formation of IEPOX-derived organic aerosol and these measurements. However, because only a subset of isoprene-derived aerosol compounds have been specifically identified in laboratory studies, our simulation of known IEPOX-derived organic aerosol compounds predicts a mass 10-fold lower than the field measurements, despite abundant gas-phase IEPOX. Sensitivity studies suggest that increasing the effective IEPOX uptake coefficient and including aerosol-phase reactions that lead to the addition of functiona...

Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds

Abstract. The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40–75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm−1 (−50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.

Influence of boundary layer dynamics and isoprene chemistry on the organic aerosol budget in a tropical forest

We study the organic aerosol (OA) budget in a tropical forest by analyzing a case that is representative for the OP3 campaign at Borneo. A model is designed that combines the essential dynamical and chemical processes that drive the diurnal evolution of reactants in the atmospheric boundary layer (BL). In this way, the model simultaneously represents the effects and interactions of various dynamical and chemical factors on the OA budget. The model is able to reproduce the observed diurnal dynamics of the BL, including the evolution of most chemical species involved in secondary organic aerosol (SOA) formation. A budget analysis of the contributions of the dynamic and chemical processes reveals the significance of the entrainment process in the diurnal evolution of SOA. Further, we perform a series of sensitivity analyses to determine the effect of meteorological forcings and isoprene chemical pathways on the OA budget. Subsidence and advection of cool air have opposing effects on the OA concentration, although both suppress BL growth. Recycling of the OH radical in the oxidation of isoprene may affect the amount of SOA that is formed, but must be understood better before its impact can be definitely determined. SOA formation from isoprene is calculated for both the low‐ and high‐NOx pathway, with the latter dominating the isoprene peroxy radical chemistry. Finally, we study the significance of SOA formation through the reactive uptake of isoprene epoxydiols on acidic sulfate aerosol. Despite the incorporation of these new pathways, the OA concentration is systematically underestimated by about a factor of 2.

Effect of relative humidity on SOA formation from isoprene/NO photooxidation: enhancement of 2-methylglyceric acid and its corresponding oligoesters under dry conditions

Abstract. The effect of relative humidity (RH) on secondary organic aerosol (SOA) formation from the photooxidation of isoprene under initially high nitric oxide (NO) conditions (i.e., isoprene/NO ~3) was investigated in a dual outdoor smog chamber. Based upon particle volume concentration measurements and the detailed chemical characterization of isoprene SOA using gas chromatography/mass spectrometry (GC/MS) and ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), enhanced SOA formation was observed under lower RH conditions (15–40 %) compared to higher RH conditions (40–90 %). 2-methylglyceric acid (2-MG) and its corresponding oligoesters, which have been previously shown to form from further oxidation of methacryloylperoxynitrate (MPAN), were enhanced in the particle-phase under lower RH conditions. In addition, an abundant unknown SOA tracer likely derived from the further oxidation of MPAN was detected and enhanced under lower RH conditions. In contrast, the 2-methyltetrols, which are known to mainly form from the reactive uptake of isoprene epoxydiols (IEPOX) under low-NO conditions in the presence of acidified aerosol, did not substantially vary under different RH conditions; however, isoprene-derived organosulfates were found to be enhanced under high-RH conditions, indicating the likely importance of the aqueous aerosol phase in their formation. Based upon the detailed chemical characterization results, particle-phase organic esterification is tentatively proposed to explain the observed enhancements of isoprene SOA mass under lower RH conditions. Alternative mechanisms explaining the enhancement of 2-MG and its corresponding oligoesters cannot be completely ruled out. This is one of only a few chamber studies that have examined the effect of RH on isoprene SOA formation. In comparison to our recent results obtained from aromatic SOA formation, the effect of RH on isoprene SOA formation is reversed. The results of this study highlight the importance of elucidating the key reactive intermediates that lead to SOA formation, especially since RH likely affects their ability in forming SOA. Furthermore, ignoring the effects of RH may significantly affect the accuracy of both regional and global SOA models.